Through-space aromatic character in excimers

Abstract

Aromaticity, though widely used to delineate diverse photochemical phenomena, remains to be examined in excimers, a fundamental and extensively studied entity in the excited states. Herein, the first theoretical evidence for the excited state through-space aromatic character in triplet state (T₁) excimers of benzene, naphthalene and anthracene is reported using multiple aromaticity descriptors based on magnetic, electronic and geometric criteria. The calculated chemical shifts and induced current densities manifest the presence of transannular π-electronic currents in the excimers. The results open up enormous research potential from exploring the possibility of through-space aromatic character in singlet excimers to its possible implications in photoexcited state processes of aromatic supramolecular systems.